Photoprotective/cosmetic compositions comprising benzotriazole-substituted polyorganosiloxanes/polyorganosilanes

ABSTRACT

Topically applicable sunscreen/cosmetic compositions well suited for enhanced photoprotection of human skin and/or hair against the damaging effects of UV-A and UV-B irradiation, particularly solar radiation, comprise a photoprotecting effective amount of a novel benzotriazole-substituted polyorganosiloxane/polyorganosilane having one of the formulae (1) to (3): ##STR1## wherein A is a monovalent benzotriazole radical which comprises an acrylate or acrylamide functional group, which is bonded directly to a silicon atom, and which has the formula (4): ##STR2##

This application is a divisional of application Ser. No. 08/555,046,filed Nov. 8, 1995 U.S. Pat. No. 5,610,257.

CROSS-REFERENCE TO COMPANION APPLICATIONS

Our copending applications Ser. No. 08/555,334 filed Oct. 10, 1995, andSer. No. 08/555,046 filed Nov. 8, 1995, both also assigned to theassignee hereof.

BACKGROUND OF THE INVENTION

1. Technical Field of the Invention

The present invention relates to novel compounds comprising short-chain,linear or cyclic diorganosiloxanes or triorganosilanes bearing at leastone benzotriazole substituent which comprises an acrylate or acrylamidefunctional group.

This invention also relates to novel cosmetic compositions for topicalapplication comprising said benzotriazole-substitutedpolyorganosiloxanes/polyorganosilanes, for the photoprotection of theskin and/or hair against ultraviolet radiation (such compositionshereinafter sometimes simply designated "sunscreen,""sunscreen/cosmetic" or "photoprotective/sunscreen" compositions).

2. Description of the Prior Art

It is known to this art that light radiation of wavelengths of from 280nm to 400 nm promotes tanning of the human epidermis, and thatirradiation of wavelengths of from 280 to 320 nm, i.e, UV-B irradiation,causes erythema and skin burns which can impair the development of anatural tan; hence, such UV-B radiation must thus be screened from theskin.

It is also known to this art that UV-A radiation, of wavelengths of from320 to 400 nm, which tans the skin, also adversely affects it, inparticular in the event of sensitive skin or skin constantly exposed tosolar radiation. UV-A irradiation causes, in particular, a loss in theelasticity of the skin and the appearance of wrinkles, promoting apremature aging thereof. Such irradiation promotes triggering of theerythematous reaction or enhances this reaction in certain individuals,and may even be the source of phototoxic or photoallergic reactions.Thus, it is desirable to also screen out UV-A radiation.

A wide variety of compounds intended for the photoprotection (UV-Aand/or UV-B) of human skin are known to this art.

Most of these are aromatic compounds displaying an absorption of UVradiation in the region from 280 to 315 nm or in the region of from 315to 400 nm, or else in both of these regions together. They are, moreoften than not, formulated in sunscreen compositions as oil-in-wateremulsions (namely, a cosmetically acceptable vehicle, carrier or diluentcomprising an aqueous continuous dispersing phase and an oilydiscontinuous dispersed phase) which contain, at various concentrations,one or more traditional lipophilic and/or hydrophilic organic sunscreencompounds comprising an aromatic function suitable for selectivelyabsorbing harmful or deleterious UV radiation. These sunscreen compounds(and the amounts thereof) are selected as a function of the desiredspecific sun protection factor (the specific protection factor (SPF)being expressed mathematically by the ratio of the irradiation timerequired to attain the erythemogenic threshold with the UV screeningagent to the time required to attain the erythemogenic threshold in theabsence of UV screening agent.)

Other than their sunscreen activity, these compounds having anti-UVproperties must also display good cosmetic characteristics in thecompositions comprised thereof, good solubility in common solvents, andespecially fats such as oils and greases, and also good resistance towater and to perspiration (durability).

Among such prior art aromatic compounds, p-aminobenzoic acidderivatives, benzylidenecamphor derivatives, cinnamic acid derivativesand benzotriazole derivatives are particularly representative. However,certain of these compounds do not display all of the properties requiredfor an acceptable UV screening agent in sunscreen compositions. Inparticular, their intrinsic screening activity may be insufficient,their solubility in the different formulations employed forphotoprotection is not always sufficiently good (fat solubility inparticular), they may not possess sufficient stability to light(photostability) and they may also display resistance to water and tosweat. It is also desirable that these sunscreen compositions do notpenetrate the skin.

Thus, in the particular case of sunscreen compounds of the benzotriazoletype, derivatives thereof have been prepared which have improvedproperties, especially in respect of their fat solubility and theircosmetic character, by effecting bonding of the benzotriazole screeninggroup via grafting (hydrosilylation) onto a macromolecular chain of thesilicone (organopolysiloxane) type. Such derivatives are described inEP-0,392,883, assigned to the assignee hereof, and are generallydenominated "silicone screening agents", but the fat-solubility of thesecompounds can still be inadequate and, furthermore, in order to providesatisfactory sunscreen properties, it is often necessary to employrelatively large amounts of these photoprotective polymers, resulting inpoor cosmetic properties in respect of the formulations comprisedthereof.

SUMMARY OF THE INVENTION

Accordingly, a major object of the present invention is the provision ofnovel benzotriazole-substituted silicone/silane sunscreen compoundswhich display improved properties, in particular in respect of theirsolubility in fats, as well as regards their cosmetic properties.

Thus, it has now unexpectedly been determined that by bonding, inparticular via hydrosilylation, one or more specific benzotriazolederivatives, namely, one or more benzotriazole compounds which comprisean acrylate or acrylamide functional group, to a particular linear orcyclic silicone chain or a particular silane, novel silicone/silanesunscreen compounds are prepared which avoid or conspicuously amelioratethe above disadvantages and drawbacks of the prior art siliconesunscreens, said novel compounds displaying, in particular, very highsunscreen activity, both in the UV-A range and in the UV-B range, verygood solubility in the common organic solvents and notably in fattysubstances such as oils, and also excellent cosmetic properties,rendering same particularly well suited for formulation intophotoprotective/cosmetic compositions for protecting the skin and/or thehair against the damaging or deleterious effects of ultravioletradiation.

Briefly, the present invention features novel compounds having one ofthe following formulae (1) to (3): ##STR3## in which the radicals R,which may be identical or different, are each a C₁ -C₁₀ alkyl, phenyl or3,3,3-trifluoropropyl radical, at least 80% by number of the radicals Rbeing methyl radicals; the radicals B, which may be identical ordifferent, are each a radical R or a radical A as defined below; theradicals R', which may be identical or different, are each a C₁ -C₈alkyl radical or a phenyl radical; r is an integer ranging from 0 to 50,inclusive, and s is an integer ranging from 0 to 20, inclusive, with theproviso that, if s is zero, then at least one of the two radicals B is aradical A; u is an integer ranging from 1 to 6, inclusive, and t is aninteger ranging from 0 to 10, inclusive, with the proviso that t+u isequal to or greater than 3; and the radical A is a monovalent radicalbonded directly to a silicon atom and which has the following formula(4): ##STR4## wherein n is an integer ranging from 0 to 3, inclusive,and the radicals X, which may be identical or different, are each a C₁-C₈ alkyl radical, a halogen atom or a C₁ -C₄ alkoxy radical; m is 0 or1, and Y is --O--, --NH--, --COO--, --O(CH₂)_(v) --COO-- or --(CH₂)_(w)--OCONH-- in which v and w are integers ranging from 0 to 12, inclusive;R is 0 or 1; g is an integer ranging from 0 to 12, inclusive; Z is --O--or --NH--; R¹ is hydrogen or a C₁ -C₄ alkyl radical; and R² is hydrogenor a methyl radical.

DETAILED DESCRIPTION OF BEST MODE AND PREFERRED EMBODIMENTS OF THEINVENTION

More particularly according to the present invention, in the aboveformulae (1) to (3), A is thus the radical derived from thebenzotriazole which, after bonding to the starting short silicone chainor to the starting silane, imparts absorbing properties to the compoundsof linear diorganosiloxane type (formula (1)), or of cyclicdiorganosiloxane type (formula (2)), or of triorganosiloxane type(formula (3)), both with respect to UV-A and UV-B radiation. Asindicated above, and as is apparent from the definition of the aboveformula (4), this group necessarily comprises either one acrylatefunction (Z=O) or one acrylamide function (Z=NH) which is provided bythe linking or bridging moiety which couples the benzotriazole to thesilicone chain or to the silane.

Also as is apparent from the above formula (4), the coupling of thelinking radical --(Y)_(m) --(CH₂ --CHR¹) _(p) --(CH₂)₁ --Z--CO--CHR²--CH₂ -- to the benzotriazole nucleus thus bonds the benzotriazolenucleus to a silicon atom of the silicone backbone or of the silane, andthis substitution can be effected at all available positions afforded bythe two aromatic rings of the benzotriazole: ##STR5##

Preferably, this coupling is at positions 3, 4, 5 (aromatic ring bearingthe hydroxyl function) or 4' (benzene ring fused to the triazolyl ring),and even more preferably at positions 3, 4 or 5.

Likewise, the coupling of the substituent X can be at all otheravailable positions of the benzotriazole. However, this coupling ispreferably at positions 3, 4, 4', 5 and/or 6.

In the above formulae (1) to (3), the alkyl radicals can be linear orbranched and are advantageously selected from among methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl,neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octylradicals. The preferred alkyl radicals R, R' and B according to theinvention are methyl, ethyl, propyl, n-butyl, n-octyl and 2-ethylhexylradicals. Even more preferably, the radicals R, R' and B are all methylradicals.

Among the compounds of the above formulae (1) to (3), preferred arethose corresponding to formula (1) or to formula (2), namely, linear orcyclic short-chain diorganosiloxanes.

Among the linear or cyclic diorganosiloxanes according to the presentinvention, preferred are the random derivatives or well-defined blockderivatives having at least one, and more preferably all of thefollowing definitions:

R is alkyl and, even more preferably, is methyl,

B is alkyl and, even more preferably, is methyl (in the case of thelinear compounds of formula (1)),

r ranges from 0 to 3, inclusive; s ranges from 0 to, 3 inclusive (in thecase of the linear compounds of formula (1)),

t+u ranges from 3 to 5 (in the case of the cyclic compounds of formula(2)),

n is not zero and is preferably equal to 1 or 2, and X is then selectedfrom among methyl, tert-butyl or C₁ -C₄ alkoxy radicals, preferably amethoxy radical,

m is not zero and Y is --O-- or

p is not zero and R

q ranges from 0 to 3, inclusive, and

Z is --O-- or --NH--.

To prepare the silicone sunscreen agents of formulae (1) and (2), afirst technique (Method 1), can be employed, namely, a traditionalhydrosilylation reaction: ##STR6## starting from the correspondingsilicone in which, for example, all of the radicals A are hydrogenatoms. This starting silicone will hereinafter be designated derivativecontaining SiH; the SiH groups may be present in the silicone backboneand/or at the ends of the silicone chain. These derivatives containingSiH are well known compounds in the silicone industry and are generallycommercially available. They are described, for example, in U.S. Pat.Nos. 3,220,972, 3,697,473 and 4,340,709.

This derivative containing SiH may thus be represented either by thefollowing formula (1a): ##STR7## in which R, X and s are as definedabove in respect of the formula (1) and the radicals B', which may beidentical or different, are selected from among the radicals R and ahydrogen atom, or by the following formula (2a): ##STR8## in which R, tand u are as defined above in respect of the formula (2).

A conventional hydrosilylation reaction is thus carried out on thisSiH-containing derivative of formula (1a) or (2a), conducted in thepresence of a catalytically effective amount of a platinum catalyst,with an organic benzotriazole compound having the following formula(4a): ##STR9## in which X, Y, Z, R¹, R², n, m, p and q are as definedabove in respect of the formula (4).

Processes suitable for the preparation of the above compounds of formula(4a) are described, in particular, in U.S. Pat. Nos. 4,316,033 and4,328,346. Moreover, certain of these compounds are commerciallyavailable. In particular,2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole is marketedunder the trademark "Norbloc 7966®" by Noramco.

In addition, the working conditions to be observed for conducting thehydrosilylation reaction between the compounds of formula (1a) or (2a)above with the compound of formula (4a) above are reported in theaforesaid EP-0,392,883, hereby expressly incorporated by reference.

As regards the photoprotective agents of the triorganosilane type offormula (3), these can be prepared via hydrosilylation reaction betweena starting silane of formula (R')₃ Si--H (formula (3a)), in which R' isas defined above in respect of the compounds of formula (3), and anorganic benzotriazole derivative of above formula (4a).

Exemplary compounds of formula according to the present inventioninclude the following:

(a) 2-(2'-hydroxy-5'-methacrylyloxyethylphenyl)-2H-benzotriazole;

(b) 5-methoxy-2-(2'-hydroxy-4'-methacrylyloxyphenyl)-2H-benzotriazole;

(c)5-methoxy-2-(2'-hydroxy-3'-tert-butyl-5'-methacrylyloxyethylphenyl)-2H-benzotriazole;

(d)5-methyl-2-(2'-hydroxy-5'-methacrylyloxyethyloxyphenyl)-2H-benzotriazole;

(e) 5-methacrylyloxyethyl-2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)-2H-benzotriazole.

Another synthesis (Method 2) which is suitable for the preparation ofthe silicone-containing sunsceen agents of formulae (1) and (2) employsstarting compounds corresponding to formula (1) or (2) in which all ofthe radicals A are replaced by the radical of formula (5): ##STR10## inwhich R² is as defined above and R³ is a hydrogen atom or a methyl orethyl radical.

The alcohol, the phenol or the amine corresponding to formula (4b):##STR11## in which X, Y, R¹, n, m, p and q are as defined above inrespect of the formula (4) and Z' is --OH or --NH₂, is then reacted withthis carboxylic siloxane derivative.

Relative to the silicone photoprotective agents of the prior art, suchas those described in EP 0,392,883, the benzotriazole-substitutedsilicone/silane sunscreen agents according to the invention exhibit oneor more essential structural differences which are the source of theirexceptional properties: the silicone chains onto which the benzotriazolestructural unit is grafter are, on the one hand, much shorter, and, onthe other, the structural unit derived from the benzotriazole alwayscomprises at least one acrylate or acrylamide functional group.

Also as indicated above, the compounds of formulae (1) to (3) aboveexcellent intrinsic screening activity with respect to UV-A and UV-Bultraviolet radiation. In addition, taking account of their highlyliposoluble nature, the compounds of formulae (1) to (3) may be used inhigh concentrations, thereby imparting very high specific protectionfactors to the final compositions; moreover, they distribute themselvesuniformly in standard cosmetic vehicles comprising at least one fattyphase or at least one cosmetically acceptable organic solvent, and maythus be applied to the skin or hair to form an effective protectivefilm. Too, their cosmetic properties are very good, namely, inparticular, compared with the silicone screening agents of the priorart, these products are less sticky and render the skin or hair softer.

Thus, the present invention also features cosmetic compositionscomprising, in a cosmetically acceptable vehicle, carrier or diluent,preferably including at least one fatty phase or at least one organicsolvent, an effective photoprotective amount of at least one compound ofthe above formulae (1) to (3).

The compounds of formulae (1) to (3) are advantageously present inproportions ranging from 0.1% to 20% by weight, and preferably from 0.5%to 10% by weight, relative to the total weight of the composition.

The cosmetic compositions of the invention may be used as compositionsfor protecting the human epidermis or hair against ultraviolet rays, assunscreen compositions or as makeup products.

These compositions may, in particular, be in the form of a lotion, athickened lotion, a gel, a cream, an ointment, a milk, a powder or asolid stick and may optionally be packaged as an aerosol, as a foam, amousse or a spray.

They can contain the usual cosmetic adjuvants and additives, such asfats and fatty substances, organic solvents, silicones, thickeners,softeners, emollients, complementary sunscreens, anti-foaming agents,moisturizing or hydrating agents, fragrances and perfumes,preservatives, surfactants, fillers, sequestering agents, anionic,cationic, nonionic or amphoteric polymers or mixtures thereof,propellants, basifying or acidifying agents, colorants, dyes, pigmentsor nanopigments, in particular those designed to provide a complementaryphotoprotective effect by physically blocking out ultraviolet radiation,or any other ingredient customarily used in cosmetics, especially forthe production of sunscreen compositions.

Exemplary of the organic solvents are the lower alcohols and polyols,such as ethanol, isopropanol, propylene glycol, glycerol and sorbitol.

The fats or fatty substances can comprise of an oil or wax or mixturesthereof, fatty acids, fatty acid esters, fatty alcohols, petrolatum,paraffin, lanolin, hydrogenated lanolin or acetylated lanolin. The oilsmay be selected from among animal, vegetable, mineral or synthetic oilsand, in particular, hydrogenated palm oil, hydrogenated castor oil,liquid petrolatum, liquid paraffin, puncellin oil, volatile ornon-volatile silicone oils, and isoparaffins.

When the cosmetic composition according to the invention are used forprotecting the human epidermis against the deleterious or damagingeffects of UV irradiation or as sunscreen compositions, they areadvantageously formulated as a suspension or dispersion in solvents orfatty substances, or, alternatively, in the form of an emulsion (inparticular of O/W or W/O type, but preferably of O/W type) such as acream or a milk, or of a vesicle dispersion, or as an ointment, a salve,a gel, a solid stick or an aerosol foam. The emulsions may additionallycontain anionic, nonionic, cationic or amphoteric surface-active agents.

When the cosmetic compositions according to the invention are used forthe photoprotection of the hair, they can be formulated as a shampoo, alotion, a gel or rinse, to be applied before or after shampooing, beforeor after dyeing or bleaching, before, during or after permanent-wavingor straightening of the hair, or as a styling or treatment lotion orgel, a blow-drying or hair-setting lotion or gel, a hair lacquer, apermanent-waving or hair-straightening composition, or a composition fordyeing or bleaching the hair.

When the cosmetic compositions according to the invention are used asmakeup products for the eyelashes, the eyebrows, the skin or the hair,such as a skin-treatment cream, a foundation, a lipstick, an eye shadow,a blush, an eyeliner, a mascara or a coloring gel, they can beformulated in solid or pasty, anhydrous or aqueous form, such asoil-in-water or water-in-oil emulsions, suspensions or gels.

The cosmetic treatment of the skin or hair to protect same against thedeleterious effects of ultraviolet radiation, in particular solarradiation, comprising topically applying to the skin or hair aneffective amount of a sunscreen/cosmetic composition as described above,or of a compound of the above formulae (1) to (3).

In order to further illustrate the present invention and the advantagesthereof, the following specific examples are given, it being understoodthat same are intended only as illustrative and in nowise limitative.

EXAMPLE 1

This example relates to the preparation (according to Method 1) of acompound in accordance with the present invention, having the structuralformula: ##STR12## in which A is the radical: ##STR13## (this compoundhas formula (1) in which R=B=CH₃ ; r=0; s=1; n=0; m=0; q=2; R² =CH₃).

30 g of 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole("Norbloc 7966®") and 50 ml of toluene were introduced into a reactor.The mixture was heated to 80° C., under nitrogen. The hydrosilylationcatalyst (complex containing 3-3.5% of Pt in cyclovinylmethylsiloxane,marketed by Huls under the trademark Petrarch PC085: 100 μl) was added,followed by 24.5 g of heptamethyltrisiloxane. After 67 hours at 80° C.under nitrogen, with 50 μl additions of catalyst every 12 hours, thereaction medium was concentrated and chromatography was then carried outon silica under pressure (eluent: heptane with a 0-50% gradient of CH₂Cl₂). 5.1 g of the desired final product, which was in the form of apale yellow oil, were thus recovered.

The UV absorption characteristics (measured in ethanol) of this compoundwere as follows:

    ______________________________________                                        λ.sub.max :337 nm                                                                           ε.sub.max :17 500                                λ.sub.max :298 nm                                                                           ε.sub.max :14 550                                ______________________________________                                    

This compound is thus a very effective sunscreen which is active in theUV-A and UV-B range.

EXAMPLE 2

This example relates to the preparation, but in this instance via Method2, of the same compound as prepared in Example 1.

(a) First stage

34.24 g of ethyl methacrylate containing a spatula-tipful of4-hydroxyanisole were heated to 80° C., under nitrogen, in a reactor.The hydrosilylation catalyst (complex containing 3-3.5% of Pt incyclovinylmethylsiloxane, marketed by Huls under the trademark PetrarchPC085: 200 μl) was added thereto, followed by dropwise addition, over 30minutes, of 73.42 g of heptamethyltrisiloxane. After stirring for 3hours at 80° C. under nitrogen, the medium was concentrated, theacrylate and the siloxane in excess were evaporated off and a paleyellow oil was thus recovered. This oil was then distilled under vacuum.The fraction distilling at 48°-52° C. at 20 mmHg corresponded to thedesired compound of formula (1) in which R=B=CH₃ ; r=0; s=1; and A wasthe radical of formula (5) wherein R² =methyl and R³ =ethyl.

(b) Second stage

340 ml of toluene, 20 g of the compound prepared in Stage (a) and 12.7 gof 2-(2'-hydroxy-5'-hydroxyethylpheny1)-2H-benzotriazole (i.e., acompound of formula (4a) in which n=0; m=0; p=1; R¹ =H; q=0 and Z'=OE)were introduced into a reactor fitted with Dean-Stark apparatus. 0.5 gof p-toluenesulfonic acid was added and the mixture was heated at refluxfor 20 hours with removal of the ethanol formed. The reaction medium wasconcentrated and chromatography was then carried out on silica underpressure (eluent: heptane with a 0-50% gradient of CH₂ Cl₂). 9.8 g ofthe desired final product, which corresponded to the compound preparedin Example 1, were thus recovered.

EXAMPLE 3

A photoprotective/sunscreen formulation in accordance with the inventionwas prepared in the form of a sunscreen cream containing:

    ______________________________________                                        (a) Compound of Example 1       5      g                                      (b) Mixture of cetylstearyl alcohol                                                                           7      g                                          and cetylstearyl alcohol oxyethylenated with                                  33 mol of EO ("SINNOWAX AO" marketed by Henkel)                           (c) Mixture of non-self-emulsifiable                                                                          2      g                                          glyceryl mono- and distearate                                             (d) Cetyl alcohol               1.5    g                                      (e) C.sub.12 -C.sub.15  alkyl benzoate                                                                        20     g                                          ("FINSOLV TN" marketed by Witco)                                          (f) Polydimethylsiloxane        1.5    g                                      (g) Glycerol                    17.5   g                                      (h) Fragrance, preservative qs                                                (i) Water qs                    100    g                                      ______________________________________                                    

This cream was formulated according to the standard techniques for thepreparation of emulsions, by dissolving the screening agent in the fattyphase containing the emulsifying agents, heating this fatty phase toabout 70°-80° C. and adding, with vigorous stirring, the water which hadbeen heated to the same temperature. Stirring was maintained for 10 to15 minutes and, after permitting the composition to cool with moderatestirring, the fragrance and preservative were lastly added at about 40°C.

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions, and changes may be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

What is claimed is:
 1. A topically applicable sunscreen/cosmeticcomposition adopted for the photoprotection of human skin and/or hair,comprising a photoprotecting effective amount of apolyorganosiloxane/polyorganosilane compound having one of the formulae(1) to (3): ##STR14## in which the radicals R, which may be identical ordifferent, are each a C₁ -C₁₀ alkyl, phenyl or 3,3,3-trifluoropropylradical, at least 80% by number of the radicals R being methyl radicals;the radicals B, which may be identical or different, are each a radicalR or a radical A as defined below; the radicals R', which may beidentical or different, are each a CC₁ -C₈ alkyl radical or a phenylradical; r is an integer ranging from 0 to 50, inclusive, and s is aninteger ranging from 0 to 20, inclusive, with the proviso that, if s iszero, then at least one of the two radicals B is a radical A; u is aninteger ranging from 1 to 6, inclusive, and t is an integer ranging from0 to 10, inclusive, with the proviso that t+u is equal to or greaterthan 3; and the radical A is a monovalent radical bonded directly to asilicon atom and which has the following formula (4): ##STR15## whereinn is an integer ranging from 0 to 3, inclusive, and the radicals X,which may be identical or different, are each a C₁ -C₈ alkyl radical, ahalogen atom or a C₁ -C₄ alkoxy radical; m is 0 or 1, and Y is --O--,--COO--, --O(CH₂)_(v) --COO-- or --(CH₂)_(w) --)CONH-- in which v and ware integers ranging from 0 to 12, inclusive; p is 0 or 1; q is aninteger ranging from 0 to 12, inclusive; Z is --O-- or --NH--; R¹ ishydrogen or a C₁ -C₄ alkyl radical; and R² is hydrogen or a methylradical, a benzotriazole-substituted in a cosmetically acceptablevehicle, carrier or diluent therefor.
 2. The sunscreen/cosmeticcomposition as defined by claim 1, said cosmetically acceptable vehicle,carrier or diluent comprising at least one fatty phase or at least oneorganic solvent.
 3. The sunscreen/cosmetic composition as defined byclaim 1, comprising an oil-in-water or water-in-oil emulsion.
 4. Thesunscreen/cosmetic composition as defined by claim 1, comprising from0.1% to 20% by weight of said photoprotecting compound.
 5. A method forprotecting human skin and/or hair against the deleterious effects ofultraviolet irradiation, comprising topically applying thereto aneffective amount of the sunscreen/cosmetic composition as defined byclaim
 1. 6. A method for protecting human skin and/or hair against thedeleterious effects of solar radiation, comprising topically applyingthereto an effective amount of the sunscreen/cosmetic composition asdefined by claim
 1. 7. The composition of claim 1, wherein the compoundhas formula (1).
 8. The composition of claim 1, wherein the compound hasformula (2).
 9. The composition of claim 1, wherein the compound hasformula (3).
 10. The composition of claim 1, where in the compound offormulae (1) or (2), the radicals R are alkyl radicals.
 11. Thecomposition of claim 10, wherein said alkyl radicals are selected fromthe group consisting of methyl, ethyl, propyl, n-butyl, n-octyl and2-ethylhexyl radicals.
 12. The composition of claim 11, wherein said Rradicals are methyl radicals.
 13. The composition of claim 7, where inthe compound of formula (1) the radicals B are alkyl radicals.
 14. Thecomposition as defined by claim 13, where in said compound of formula(1) radicals B are selected from the group consisting of methyl, ethyl,propyl, n-butyl, n-octyl and 2-ethylhexyl radicals.
 15. The compositionof claim 14, where in said compound of formula (1) said radicals B aremethyl radicals.
 16. The composition of claim 7, where in the compoundof formula (1), r ranges from 0 to 3 and s ranges from 0 to
 3. 17. Thecomposition of claim 8, where in in the compound of formula (2), t+uranges from 3 to
 5. 18. The composition of claim 9, where in in thecompound of formula (3), the radicals R' are selected from the groupconsisting of methyl, ethyl, propyl, n-butyl, n-octyl and 2-ethylhexylradicals.
 19. The composition of claim 18, said R' radicals being methylradicals.
 20. The composition as defined by claim 1, where in theformulae (1) to (3), n s other than zero and the radicals X are selectedfrom the group consisting of methyl, tert-butyl and C₁ -C₄ alkoxyradicals.
 21. The composition of claim 20, wherein said radicals X aremethyl or methoxy radicals.
 22. The composition as defined by claim 21,wherein said radicals X are methoxy radicals.
 23. The composition ofclaim 1, where in the compound of formulae (1) to (3), m is other thanzero and Y is --O-- or --NH--.
 24. The composition as defined by claim1, where in the compound of formulae (1) to (3), p is other than zeroand R¹ is hydrogen.
 25. The composition of claim 1, where in thecompound of formulae (1) to (3), g ranges from 0 to
 3. 26. Thecomposition of claim 1, wherein in the formula (1) to (3), the radical--(Y)_(m) --(CH₂ --CHR¹)p--(CH₂)q--Z--CO--CHR² --CH₂ -- is bonded to the3-, 4-, 4'-, or 5-position of the benzotriazole nucleus.
 27. Thecomposition of claim 26, said bonding being to the 3- , 4- or 5-positionof the benzotriazole nucleus.
 28. The composition as defined by claim 1,where in the compound of formulae (1) to (3), the radical(s) X is/arebonded to the 3-, 4-, 4'-, 5- and/or 6-positions of the benzotriazolenucleus.
 29. The method of claim 5, wherein the composition comprises acompound having the formula (1).
 30. The method of claim 5, wherein thecomposition comprises a compound having the formula (2).
 31. The methodof claim 28, wherein the composition comprises a compound having theformula (3).
 32. The method of claim 29, wherein the compositioncomprises a compound having the formula (1).
 33. The method of claim 29,wherein the composition comprises a compound having the formula (2). 34.The method of claim 29, wherein the composition comprises a compoundhaving the formula (3).